EP0505692A1 - Verfahren zur Herstellung gereinigter Alkansulfonsäuren - Google Patents

Verfahren zur Herstellung gereinigter Alkansulfonsäuren Download PDF

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Publication number
EP0505692A1
EP0505692A1 EP92101629A EP92101629A EP0505692A1 EP 0505692 A1 EP0505692 A1 EP 0505692A1 EP 92101629 A EP92101629 A EP 92101629A EP 92101629 A EP92101629 A EP 92101629A EP 0505692 A1 EP0505692 A1 EP 0505692A1
Authority
EP
European Patent Office
Prior art keywords
alkanesulfonic acid
acid
aqueous
chlorine
crude aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92101629A
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English (en)
French (fr)
Other versions
EP0505692B1 (de
Inventor
Phyllis Ann Henderson
Carl Postuma
Steven Gabriel Schon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema Inc
Original Assignee
Elf Atochem North America Inc
Atochem North America Inc
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Publication of EP0505692A1 publication Critical patent/EP0505692A1/de
Application granted granted Critical
Publication of EP0505692B1 publication Critical patent/EP0505692B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/04—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention concerns the purification of crude aqueous alkanesulfonic acid containing oxidizable impurities. More particularly, it relates to the use of chlorine treatment of such crude material to convert the oxidizable impurities to alkanesulfonyl chloride and thereafter hydrolysing the alkanesulfonyl chloride to alkanesulfonic acid.
  • alkanesulfonic acid In the manufacture of alkanesulfonic acid by the reaction of an alkyl mercaptan or dialkyl disulfide with chlorine and aqueous hydrochloric acid at elevated temperature, a crude aqueous (20-35 wt. % water) alkanesulfonic acid containing oxidizable impurities is first formed.
  • Dialkyl disulfide, alkyl alkane thiosulfonate and alkanesulfonyl chloride are the principal stable intermediates in this process.
  • the total of dialkyl disulfide and alkyl alkane thiosulfonate is referred to as oxidizable impurities in the crude aqueous product.
  • the crude product may be purified by heat stripping.
  • Heat stripping usually steam stripping, removes some of the oxidizable impurities overhead from the crude product but unexceptable levels remain and the bottoms product of the stripper must be further treated, e.g., by reaction with hydrogen peroxide or ozone, to reduce or eliminate the impurities.
  • Figure 1 of the drawing is a flow diagram of the preferred form of the process of the invention.
  • This invention is a process of preparing purified C1-C8 alkanesulfonic acid from crude aqueous C1-C8 alkanesulfonic acid containing oxidizable impurities, said process comprising treating said crude aqueous alkanesulfonic acid with chlorine in an amount effective to convert oxidizable impurities to the corresponding alkanesulfonyl chloride, and hydrolyzing said alkanesulfonyl chloride to alkanesulfonic acid.
  • This invention relates to the use of chlorine to convert the oxidizable impurities in crude aqueous C1-C8 alkanesulfonic acid to alkanesulfonyl chloride and thereafter hydrolyzing the alkanesulfonyl chloride to alkanesulfonic acid thereby providing a purer alkanesulfonic acid product.
  • the preparation of the crude aqueous alkanesulfonic acid is usually through the reaction of a C1-C8 alkyl mercaptan or C1-C8 alkyl disulfide and chlorine in the presence of aqueous hydrochloric acid at elevated temperature.
  • While the process is applicable to C1-C8 alkanesulfonic acid including for example methane, ethane, propane, butane, propane, hexane, heptane and octanesulfonic acid, it is preferably used in the purification of crude aqueous C1-C4 alkanesulfonic acid and most preferably crude aqueous methanesulfonic acid (MSA) and, hereinafter, the purification of crude aqueous MSA will be used to demonstrate the invention.
  • MSA crude aqueous methanesulfonic acid
  • the purification process of this invention is used for the treatment of crude aqueous MSA (20-35 weight % H20) prepared by the reaction of methyl mercaptan with chlorine in the presence of aqueous hydrochloric acid at an elevated temperature ranging from about 85 to 115°C, more preferably about 95 to 105°C and typically about 98°C.
  • the crude aqueous MSA recovered from this process contains appreciable quantities of stable intermediates including dimethyl disulfide (DMDS), methyl methane thiosulfonate (MMTS) and methanesulfonyl chloride (MSC).
  • DMDS dimethyl disulfide
  • MMTS methyl methane thiosulfonate
  • MSC methanesulfonyl chloride
  • the total of the DMDS and MMTS is referred to as oxidizable impurities in the product specifications.
  • crude aqueous MSA containing oxidizable impurities is treated with chlorine in an amount sufficient to convert said oxidizable impurities to MSC and the MSC containing aqueous MSA is subjected to sufficient heat to hydrolyze the MSC to MSA.
  • the amount of chlorine used will depend on whether the crude MSA is treated with chlorine as a part of a batch process or as a part of a continuous process.
  • the crude aqueous MSA is preferably saturated with chlorine while in the continuous process for making and purifying aqueous MSA, small quantities (preferably 0.1% to 0.8% based on the weight of crude aqueous MSA) are injected into the discharge piping of a reactor producing, e.g., from 1000-1500 pounds per hour of crude aqueous MSA.
  • the chlorine is preferably sparged into the discharge tubing close to the bottom of the reactor to ensure that any unreacted chlorine will flow into the reactor to be used in the formation of the crude aqueous MSA from mercaptan.
  • the crude aqueous MSA is conventionally passed to a steam stripper or the like to remove undesirable contaminates from the crude aqueous MSA. Chlorides, DMDS, MMTS, MSC, MSA, water and non-condensed chlorine are removed overhead, and an aqueous MSA with substantially reduced oxidizable impurities is recovered as a bottoms product.
  • MSC which is produced by the conversion of oxidizable impurities with chlorine, is hydrolyzed in the steam stripper to MSA.
  • a finishing reactor which subjects the MSC in the crude aqueous MSA to sufficient heat for a sufficient time to convert the MSC to MSA, may be employed.
  • the product of the finishing reactor may then be subjected to steam stripping, if desired.
  • While the chlorination of the crude aqueous MSA is preferably carried out in the discharge line or piping, as close as possible to the reactor, beneficial purification results may be obtained by sparging chlorine into the crude at any point in the process subsequent to discharge from the reactor so long as the chlorine makes adequate contact with the oxidizable impurities to react therewith to form MSC and the MSC can be hydrolyzed to MSA.
  • Line 22 in Figure 1 of the drawing shows an alternative point of injection of chlorine into the aqueous MSA.
  • the purified aqueous MSA is further treated to remove substantially all water, for example, by the evaporation procedures of U.S. patents No's. 4,450,047 or 4,938,846.
  • Aqueous methanesulfonic acid (30 wt. % H2O) samples containing several hundred ppm of oxidizable impurities were chlorinated in batch operations by saturating the test samples with chlorine and allowing the chlorine to react with the impurities in the sample for from 48 to 72 hours.
  • the aqueous MSA was then air stripped to remove excess chlorine.
  • the batch chlorination reduced the oxidizable impurity content of the MSA samples to zero.
  • reactor 2 with sidearms used for reactant recycling and temperature control was operated at atmospheric pressure and a temperature of 98 o C to react methyl mercaptan entering the reactor at the rate of 475 pounds per hour through line 4 and chlorine entering the reactor at the rate of 2100 pounds per hour through line 6.
  • Crude aqueous MSA (at a concentration of 70 weight percent MSA) was discharged at the bottom of reactor 2 through line 12 at the rate of about 2.2 GPM (gallons/minute) while hydrogen chloride vapors were vented at the top of reactor 2 through line 8.
  • the crude aqueous MSA discharged through line 12 contained an average amount of oxidizable impurities in excess of 156 ppm.
  • chlorine was sparged into the crude through line 10 positioned close to the bottom of reactor 2 at a rate of about 20 standard cubic feet per minute (0.26% based on the weight of the crude aqueous MSA). Thereafter, the chlorine treated crude was pumped to the top of steam stripper 14 which was operated at a top temperature of 118-125°C by injecting super-heated steam (227°C) near the bottom through line 16.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Enzymes And Modification Thereof (AREA)
  • Steroid Compounds (AREA)
EP92101629A 1991-03-27 1992-01-31 Verfahren zur Herstellung gereinigter Alkansulfonsäuren Expired - Lifetime EP0505692B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/676,143 US5583253A (en) 1991-03-27 1991-03-27 Method of preparing purified alkanesulfonic acid
US676143 1991-03-27

Publications (2)

Publication Number Publication Date
EP0505692A1 true EP0505692A1 (de) 1992-09-30
EP0505692B1 EP0505692B1 (de) 1995-11-02

Family

ID=24713394

Family Applications (1)

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EP92101629A Expired - Lifetime EP0505692B1 (de) 1991-03-27 1992-01-31 Verfahren zur Herstellung gereinigter Alkansulfonsäuren

Country Status (12)

Country Link
US (1) US5583253A (de)
EP (1) EP0505692B1 (de)
JP (1) JPH0597792A (de)
KR (1) KR920018017A (de)
AT (1) ATE129699T1 (de)
AU (1) AU646716B2 (de)
CA (1) CA2060022A1 (de)
DE (1) DE69205713T2 (de)
FI (1) FI921334A (de)
IE (1) IE920222A1 (de)
IL (1) IL100872A0 (de)
TW (1) TW216786B (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT407117B (de) * 1997-09-19 2000-12-27 Immuno Ag Fibrinschwamm
EP1644558A1 (de) * 2003-05-12 2006-04-12 Arkema Inc. Hochreine elektrolytische sulfonsäurelösungen
EP1773752A2 (de) * 2004-08-05 2007-04-18 Arkema Inc. Entfernen von alkylalkansulfonatestern aus alkansulfonsäuren und anderen organischen medien
CN103145592A (zh) * 2013-02-20 2013-06-12 上海晶纯实业有限公司 离子对色谱专用试剂十二烷基磺酸钠的纯化工艺
US9399618B2 (en) 2003-05-12 2016-07-26 Arkema Inc. High purity electrolytic sulfonic acid solutions
WO2017080994A1 (de) 2015-11-10 2017-05-18 Basf Se Verfahren zur wiederaufarbeitung von alkansulfonsäure
WO2018192954A1 (en) 2017-04-18 2018-10-25 Basf Se Process for purifying alkanesulfonic anhydride and process for producing alkanesulfonic acid using the purified alkanesulfonic anhydride
US10577312B2 (en) 2015-11-10 2020-03-03 Basf Se Process for purifying alkanesulfonic acids

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4441726B2 (ja) * 2003-01-24 2010-03-31 石原薬品株式会社 スズ又はスズ合金の脂肪族スルホン酸メッキ浴の製造方法
FR2935142B1 (fr) * 2008-08-20 2010-11-19 Arkema France Dimethyldisulfure issu au moins partiellement de matieres renouvellables
KR101813706B1 (ko) 2014-12-04 2017-12-29 주식회사 엘지화학 무연신 폴리프로필렌계 필름
US11247967B2 (en) 2018-02-07 2022-02-15 Basf Se Process for the manufacturing of alkanesulfonic acids

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1350328A (en) * 1971-05-28 1974-04-18 Pennwalt Corp Method for the preparation of alkane sulphonic acids
EP0040560A1 (de) * 1980-05-16 1981-11-25 Societe Nationale Elf Aquitaine (Production) Herstellung von Alkan-Sulfonyl-Chloriden
EP0373305A1 (de) * 1988-12-12 1990-06-20 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Reinigung von Alkansulfonsäuren mit Ozon

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3626004A (en) * 1967-12-07 1971-12-07 Pennwalt Corp Method of preparing alkyl sulfonyl chloride
US4450047A (en) * 1983-01-28 1984-05-22 Penwalt Corporation Process for recovering anhydrous alkanesulfonic acids by reduced pressure, falling film evaporation
US4938846A (en) * 1986-12-08 1990-07-03 Atochem, North America, Inc. Preparation of anhydrous alkanesulfonic acid
FR2611708B1 (fr) * 1987-02-25 1989-06-09 Elf Aquitaine Procede de production d'acides alcane-sulfoniques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1350328A (en) * 1971-05-28 1974-04-18 Pennwalt Corp Method for the preparation of alkane sulphonic acids
EP0040560A1 (de) * 1980-05-16 1981-11-25 Societe Nationale Elf Aquitaine (Production) Herstellung von Alkan-Sulfonyl-Chloriden
EP0373305A1 (de) * 1988-12-12 1990-06-20 ATOCHEM NORTH AMERICA, INC. (a Pennsylvania corp.) Reinigung von Alkansulfonsäuren mit Ozon

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 79, no. 3, 23 July 1973, Columbus, Ohio, US; abstract no. 18083V, R. ODA ET AL.: 'Methanesulfonic acid.' page 402 ;column 2 ; *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT407117B (de) * 1997-09-19 2000-12-27 Immuno Ag Fibrinschwamm
EP1644558A1 (de) * 2003-05-12 2006-04-12 Arkema Inc. Hochreine elektrolytische sulfonsäurelösungen
EP1644558A4 (de) * 2003-05-12 2007-03-21 Arkema Inc Hochreine elektrolytische sulfonsäurelösungen
US9399618B2 (en) 2003-05-12 2016-07-26 Arkema Inc. High purity electrolytic sulfonic acid solutions
EP1773752A2 (de) * 2004-08-05 2007-04-18 Arkema Inc. Entfernen von alkylalkansulfonatestern aus alkansulfonsäuren und anderen organischen medien
EP1773752A4 (de) * 2004-08-05 2008-04-23 Arkema Inc Entfernen von alkylalkansulfonatestern aus alkansulfonsäuren und anderen organischen medien
CN103145592B (zh) * 2013-02-20 2014-09-17 上海晶纯生化科技股份有限公司 离子对色谱专用试剂十二烷基磺酸钠的纯化工艺
CN103145592A (zh) * 2013-02-20 2013-06-12 上海晶纯实业有限公司 离子对色谱专用试剂十二烷基磺酸钠的纯化工艺
WO2017080994A1 (de) 2015-11-10 2017-05-18 Basf Se Verfahren zur wiederaufarbeitung von alkansulfonsäure
US10214485B2 (en) 2015-11-10 2019-02-26 Basf Se Method of reprocessing alkanesulfonic acid
US10577312B2 (en) 2015-11-10 2020-03-03 Basf Se Process for purifying alkanesulfonic acids
WO2018192954A1 (en) 2017-04-18 2018-10-25 Basf Se Process for purifying alkanesulfonic anhydride and process for producing alkanesulfonic acid using the purified alkanesulfonic anhydride
US10730827B2 (en) 2017-04-18 2020-08-04 Basf Se Process for purifying alkanesulfonic anhydride and process for producing alkanesulfonic acid using the purified alkanesulfonic anhydride

Also Published As

Publication number Publication date
CA2060022A1 (en) 1992-09-28
IE920222A1 (en) 1992-10-07
FI921334A (fi) 1992-09-28
JPH0597792A (ja) 1993-04-20
TW216786B (de) 1993-12-01
US5583253A (en) 1996-12-10
KR920018017A (ko) 1992-10-21
EP0505692B1 (de) 1995-11-02
IL100872A0 (en) 1992-11-15
DE69205713D1 (de) 1995-12-07
DE69205713T2 (de) 1996-04-11
ATE129699T1 (de) 1995-11-15
AU646716B2 (en) 1994-03-03
AU1044992A (en) 1992-10-01
FI921334A0 (fi) 1992-03-26

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